1,2,3,4-tetrachlorbutane as a black carpet beetle larvacide



Dec. 2, 1952 l,2,3,4-TETRACHLORBUTANE AS A BLACK CARPET BEETLE LARVACIDE IOO PER CENT KILL H. JOHNSON ET AL 2,620,291

Filed Dec. 26, 1947 |,2,3,4- TETRACHLOROBUTANE P'DICHLOROBENZENE OONC'N. MGJ LITER INVENTORS HERBERT L. JOHNSON RCHIBALD F! STUART ATTORNEYS Patented Dec. 2, 1952 1,2,3,4-TETRACHLORBUTANE AS A BLACK CARPET BEETLE LARVACIDE Herbert L. Johnson, Media, and Archibald P.

Stuart, Norwood, Pa., assignors to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey Application December 26, 1947, Serial No. 793,800

2 Claims.

This invention relates to a novel larvacide and to a composition of which the larvacide is an essential ingredient.

The larvacide of this invention is l,2,3,4-tetrachlorobutane, a chemical compound, which has been known in the chemical literature for some time. Thus, 1,2,3A-tetrachlorobutane was first prepared by Henninger, Ann. Chim. (6'), 7, 229 (1886). Another preparation of this compound has been described by Muskat 8: Northrup, J. Am. Chem. Soc. 52, 4043-4055 (1930). This preparation involves the chlorination of butadiene. At least two isomers of 1,2,3,4-tetrachlorobutane have been isolated. One isomer, a liquid (B. P. 110 C.-111 C. at 40 mm. Hg) and another a solid (B. P. 130 C.134 C. at 40 mm. Hg, M. P. 72 C.) have been identified.

According to this invention we have found that both the solid and liquid forms or isomers of 1,2,3, l-tetrachlorobutane are useful as larvacides of an ellectiveness not at all expected and indeed wholly surprising.

It is well known that carpet beetles are extremely difficult to kill, particularly is this so, because the materials heretofore used as a larvacide have been ineifective to produce a suflicient kill within a reasonably short time. This has allowed the larvae to develop an actual immunity resulting in almost all cases in a virtually complete failure or ineffectiveness of the materials employed. For a more complete rsum of just how serious the matter of finding an effective larvacide has been prior to this writing reference is made to the article entitled Carpet-Beetle Control- Unsolved Wool Problem by Henry N. Mitchell published in Textile World November 19 .6, pages 170, 221 and 222.

It is generally believed that p-dichlorobenzene is a superior larvacide particularly against the carpet beetle. So far is this true that the ofiicial test larvacide now employed by the commercial testing laboratories is p-dichlorobenzene. It is to be noted that compounds having a rather good kill of the carpet beetle are extant. However, these have properties which prohibit their use, particularly for domestic purposes. It is well known that additionally to kill, a larvacide must not have a disagreeable vapor or odor and particularly that its vapor must :be non-poisonous to humans.

Comparison of the results of tests made using p-dichlorobenzene, on the one hand, and the tetrachlorobutane of this invention, on the other, made in the table below clearly shows the greatly superior quality of tetrachlorobutane whether its solid or liquid form is used.

The test procedure employed was as follows:

A two mg. of sample and of p-dichlorobenzene was weighted into separate half gallon bottles, and the bottles quickly corked. A ventilated capsule containing fifty of the Attagenus larvae and a one square inch disc of cream flannel test cloth was suspended from each cork near the center of the bottle.

The bottles were kept in an incubator at 78 F.- 80 F. for two weeks. They were inverted twice daily for several days to distribute the fumes. The test sample and the p-dichlorobenzene vaporized completely within two days.

The cloth discs were examined for injury at the end of the two weeks, and the insects were removed to recovery dishes. Four weeks later, live and dead insect were counted.

Some test results obtained are summarized in the table.

In the figure of the drawing there is shown a plot of the comparative insecticidal action of 123,4-tetrachlorobutane, on the one hand, and p-dichlorobenzene, on the other, against the yellow Attagenus (black carpet beetle) larvae. It is at once apparent from the graph that 1,23,4- tetrachlorobutane is vastly superior in kill to p-dichlorobenzene against the larvae. Thus, tetrachlorobutane will kill from 50% (at total kill) to 400% (at low kill) more larvae under the same conditions as will 'p-dichlorobenzene. It follows that much less 1,2,3,4-tetrachlorobutane is required to give the same degree of kill as pdichlorobenzene.

The larvacide of this invention can be made up for use in solution and applied in effective concentration to the material to be protected. Thus, the larvacidal ingredient of this invention can be applied to materials during a dry cleaning operation employing any desired effective concentrations of the tetrachlorobutane in a dry cleaning solvent such as dry cleaning naphtha (Stoddard solvent) or the halogenated dry cleaning solvents. Obviously, the more concentrated the solution the reater will be the quantity of tetrachlorobutane deposited in the material. The liquid tetrachlorobutane is substantially infinitely soluble in solvents such as carbon tetrachloride, trichloroethylene and dry cleaning naphthas. The solid form i also soluble in these solvents, though to a lesser extent which however is great enough to allow for proper larvacidal protection to be imparted during dry cleaning employing these solvents. The larvacidal composition of the invention can also take the form of a sub-divided solid admixture of the solid tetrachlorobutane with an inert solid carrier or the form of a subdivided inert carrier which has been contacted or impregnated with the liquid tetrachlorobutane. Such solid carriers may be, pyrophillite, talc or other well known insecticide carriers.

We claim:

1. The method of controlling damage by larvae which comprises applying l,2,3,4-tetrachlorobutane to loci infested with black carpet beetle larvae.

2. The method of controlling damage by larvae 4 which comprises contacting, within a confined space, vaporized 1,2,3,4-tetrachlorobutane With loci infested with black carpet beetle larvae. HERBERT L. JOHNSON. ARCHIBALD P. STUART.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,078,458 Remy Apr. 27, 1937 2,351,359 Mitchell June 13, 1944 15 2,419,021 Harnden Apr. 15, 1947 2,421,507 Jones June 3, 1947 OTHER REFERENCES Eddy et al., Jr. Econ. Entom,, December 1946,

20 pages 763 to 767. 

1. THE METHOD OF CONTROLLING DAMAGE BY LARVAE WHICH COMPRISES APPLYING 1,2,3,4-TETRACHLOROBUTANE TO LOCI INFESTED WITH BLACK CARPET BEETLE LARVAE. 